Interpolymers of a difluorodichloroethylene, a 1, 3-butadiene hydrocarbon and vinylidene chloride



this rangewe have found,

Patented Oct. 27, 1 953 INgTERPOLYMERS or a DIFLUORODICHLO- RQETHYLENE,A 1,3-BUTADIENE HYDRO- CARBON AND VINYLIDENE CHLORIDE Vernon L. Full:and Earl J Carlson, Akron, Olflo, assignors to The B. RGoodrich Company,New York, N. Y'., a corporation of New York No. Drawing. ApplicationJune. a, 1952, Serial No. 291,579

6 Q aima. 2 -80 invention relates to novel polymeric mats ia sand eates.- pa icula to i r olym rs Qfi-a difluorodichloroethylene a1,3.-.butadiene hy- Qtaserbon a d v nr d n de, d the P nati n her It. iswell known that many high-molecular thermoplastic; materials such aspolyvinyl chloride; must. ordinarily be mixed with. a plasticizerinorder; to, torm useful flexible. products therefrom. It i @150 knownthatsuch mechanical mixtures, have spyeral undesirable characteristics Eonexample plasticizers. such as the organic esters, tendto. migrate,absorb foreign materials whic qi-ts s o e Composition, illd i be ea hedout o the plastic posit under-certainservice conditions. Therei or an;object of this; invention to prepare r19 materials on a plasticnaturethat may be used as: such; preparing flexible products, thuseliminating the, undesirable efiects accom- R l n use o e as siscm. he jc s will appe rjh r na t r-l We have now discoyered that these objectsare atiain n a. new nd se ul lasso h h-m0- le ular weight h mq as icma ra s which ar that small variation in the monomer feed ratio of. thedifluorodichloroethylene and vinylidene chloride result in largedifierences in degree in physical properties oi the, resultinginterpolym'ers. For example, by polymerizing in aqueous emulsionamonomer mixture of 30 mol percent I,3-- butadiene, 50: mol percent1,1-difluoro-2 ,2-di,-' chloroethylene and. 20 mol percent vinylidn'chloride, we are able to prepare a plastic interpolymer resembling. in.its stress-strain characteristics ahigh-molecular weight polyethyleneintprpolymens; o; ('1); a difflnorodichloroethylene,

preferably 1 1;difluoro r2,2-dichloroethylene (-29 a utedi ne y rqs rb mn c er blr-wutadiene itself, and (3) vinylidene chloride v n. n sna inthe ntsr qlvm rs at this nv tidn a monomeric mixture. composed. of.from. 3.5.

to 55 mol percent of the difluorodichloroethylene,

25 to mol percent of the 1,3-butadienahydro-J- carbon and 10 to 35 mol"percent of vinylidene;

chloride is polymerized by any of the free radical techniques knowntoand utilized by those skilled in the art. The resulting: polymer isfreed of the reaction media and dried, The solid interpolymers soobtained are high-molecular weight plastics which are-tough, clear-,-flexible,- am r stant. and q teu expectedly have very w,. m nent-set ales. Th y nor o dy f retch t. exhibit; apid e y a clarity immediatelyafter rupture, The interpolymers or this invention have a. Wide, varietyil hr ica rp n rti s ranging from softifl'exible.

materials to} stifi; leatherlike materials. They conta r m .20 o. .0;mol? n rce t. hound. d1.- i q dichlom hylenei I The; preierred';interpolymers w of; this. invention are those prepared by, polymerizinga.three-comcorset. onomer mixtur I conta n n from to *mo1 percent1;l;di1?luoro 2;2&.dichloroethyl- 11 9 in :5. 1. .0. percent. i lid ne.chlorid a; heatre merner ent.La utadiener W thin quite unexpectedly,

plastic. We are also. able. to prepare by means of the emulsionpolymerization of a; monomer mixture, of 30 mol. percent 1,3fbutadiene,,3715 Incl percent l,l-difluoro-2,2-dichloroethylene,and 32.5 molpercent, vinylidene, chloride a plastic. interpolymer resembling. in itsstress-strain characteristics a highly plasticized polyvinyl chloridecomposition.

Preferred embodiments of the invention are illustrated in thefollowingexamples in which parts are -parts Icy-Weight;

Examples 1- through 12'- In theseexamples: mixtures: ot- IaL-difiuotd-212 -dichloroethy1ene, 133'-butadierret and: vinylie done chloride arepolymerized at 50 C;-.in= aqua-'- ousemulsion using potassium:persulfate as;in:i:-' tiat'or-,- to form plasticinterpolynrers by the:iotlowing general procedure Int'o a: pressnr'e reacvtion vessel equippedwith meansforagitationand temperature control is charged; a, soapsolution consisting. of 4001 parts of. water and 4 partswt a; fatty acidsoap,.1 .2 parts of tertiary dbdecyl mercaptan and 0.6 part of potassiumpersulfate dissol'vedi'n a.smal1 amount of water. 'Iheves about or c.

selg is flushed well with nitrogen and cooled to 100 parts'z'of amonomeric mixture is charged into the cooled reaction vessel. The

reactor is sealed" and its contents heated to 50 and the. reactionallowed to proceedwith agitation, to the desired degree of conversion.of monomer to polymer whereupon. the: reaction, is stopped. either byadding. 0.1. part; of. hydroqui; none to; the. Insulting:v latex or. by.venting, and emptying, the. reactor andv immediately coagulating thesolid polymer by the addition otmetlianol totharcsulting latex.

Aftercoagulation the. solid polymer. iswashed well with? water andd'riedat ahouti C1 The solid interpolymers so obtained are formed' intosheets. by; either milling or. molding; under. heat and; pressure;v Themonomer ratiosiused',lin mole percent, the degree of. conversion.impercent'l and the test results for each. of thaseveral. examples areshown in the following data table:

Monomer Reac 01 001; Exam 1e ratio, V1ny11- tion Converin Yield 1Tensile Elon- Brittle Permanumbgr mol per- CF20 Cl; dene time sion,polymer, point, strength, gation, point, nent set, cent 1,3 chloridehour's percent mol perp. s. l. p. s. 1. percent 0. percent butadienecent 30 37. 5 32. 5 10 24. 2 29. O6 302 l, 640 372 15 30 37. 5 32. 5 2454. 7 26. 64 l, 778 1, 888 263 7. 5 3O 40. 30.0 10 25. 2 32. 47 8352,092 385 30 40. 0 30.0 24 40. 4 29. 42 l, 360 l, 596 248 7. 5 30 42. 527. 5 27. 0 33. 70 952 2, 532 491 30 42. 5 27. 5 24 42. 4 31. 99 2, 1852, 215 218 0 30 45. 0 25. 0 10 20. 0 33. 21 l, 012 2, 336 423 5 30 45.025. 0 24 48. 2 33. 60 2, 098 2, 565 320 7. 5 30 47. 5 22. 5 10 28. 4 35.44 2, 294 2, 325 337 .5 30 47. 5 22. 5 24 45. 4 35. 18 2, 619 2, 698 3227. 5 30 50. 0 20.0 10 29. 7 36.78 3, 164 2, 300 144 7. 5 30 50. 0 20. 024 47. 3 38. 2, 91 4 2, 294 222 7. 5 13-20 The point in the tensionmeasurement atwhioh there is rapidly increasing elongation with littleincrease in the load applied.

These examples illustrate very clearly the variety of propertiesobtained in these interpolymers with only minor variations in the ratioof 1,1-difluoro- 2,2-dichloroethylene and vinylidene chloride, and inthe degree of conversion. All of the interpolymers or these examples areclear, tough, flexible materials. The interpolymer of Example 4, whichhas a low yield point, resembles highly plasticized polyvinyl chloridein its properties. The polymer of Example 11 with a high yield pointresembles high-molecular weight polyethylene in its properties. Thoseinterpolymers made from monomer mixtures containing more than 45 molpercent l,1-difluoro-2,2-dichloroethylene generally have two yieldpoints, an upper and a lower point, the upper point being given in thedata table above. The tensile strength and yield points may generally beincreased by increasing the degree or" conversion. The unexpectedly lowpermanent set values obtained on these plastic materials is Wellillustrated by Examples 5 and 11.

Examples 13 through 15 The effect of variation in the monomer ratio of1,3-butadiene and 1,1-difluoro-2,2-diohloroethylene is demonstrated inthese examples. These polymerizations are conducted at 50 C. in thepresence of 2.5 parts by weight of a fatty acid soap, 0.6 part of atertiary dodecyl meroaptan and 0.3 part of potassium persulfate, inessentially the same manner as is outlined in Examples 1 through 12.

quired for the preparation of the interpolymers of this invention. Theinterpolymers may be prepared by any of the techniques known to and usedby those skilled in the art such as bulk, solution, suspension andemulsion. Aqueous emulsion or suspension polymerizations are preferredfor practical reasons of cost and ease of operation in the preparationof the solid interpolymers. For polymers intended as adhesives and forcoatings, solution polymerization may be preferred. The interpolymersmay be prepared by batch or continuous processes and advantage may betaken of monomer proportioning techniques.

The polymerization reactions may be initiated by any of the free radicalforming initiators ordinarily used, such as the oxygen-containingpercompounds represented by potassium persulfate, benzoyl peroxide,oumene hydroperoxide and the like; the catalyst being oil or watersoluble, depending upon the nature of the polymerization systememployed. The so-called Redox systems consisting of reducing-oxidizingcouples may be used, especially at the lower temperatures ofpolymerization. Reducing agents employed in such systems may bepolyamines, sugars, heavy metal complexes and the like, and theoxidizing agents employed may be the initiators listed above as Well ashydrogen peroxide, t-butyl hydroperoxide, terpene hydroperoxides and thelike. The azo materials such as alpha, alpha-azodiiso butyronitrile alsomay be profitably employed as initiators.

The temperature at which the polymerization Monomer Exam 1e ratio, molVinyli- Yield Tensile Elon- E lastio numbper percent OFzCClQ dene point,strength, gatlon, modulus, Appearance 1, chloride p. s. l. p. s. 1.percent p. s. i. butadiene 40 10 322 1, 790 605 1, 728 Slightly rubbery.40 50 10 l, 654 3, 432 640 10, 570 Stifileathery. 30 e0 10 3, 510 3, 172519 34, 300 Boardyslightly.

Flexible.

It'is seen that decreasing the amount of 1,3- butadiene in the monomerfeed and increasing correspondingly thel,l-difiuoro-2,2'dichloroethylene content results in interpolymers withhigher yield points and ultimate tensile strengthsreaction is conductedmay be any desired in the normal ranges ordinarily employed by thoseskilled in the art such as from 0 to C. For

practical purposes the interpolymers are preferably prepared attemperatures from 40 to 60 C.

Emulsifiers for emulsion polymerization systems may be fatty acid, rosinacid or amine soaps; alkyl, aryl, aralkyl sulfonates or sulfates ormixtures thereof and the like. The potassium soaps are preferred for lowtemperature polymerizations. Concentrations of from 1 to 5 parts byWeight of emulsifier per parts of monomer are adequate and arepreferred. Y

For suspension systems, agents like gelatin,

casein, clay and polyvinyl alcohol may be used alone or in conjunctionwith small amounts of a surface-active agent. The amount used willdepend upon the type and degree of agitation employed, as is well known;and 0.1 to 0.5 part are usually employed.

The polymerization reactions may be stopped at any desired degree ofconversion by the addition of reducing agents such as a hydroquinone,preferably one of the non-discoloring derivatives, or by coagulating thepolymer as rapidly as possible. Small amounts, usually about 0.1 part ofthe reducing agents are employed. The coagulation is efiected generallyby the addition of solvents such as alcohol, acetone and the like, butthe interpolymer may be freed from the reacting media by salt-acidcoagulation.

The solvents and diluents utilized in solution polymerization will bedetermined by the end result desired. If a solution of the interpolymeris desired, an aromatic solvent such as benzene may be used. If it isdesired that the interpolymer separate on forming, non-solvents such asbutane or hexane may be employed. This selection is well known to thoseskilled in the art.

Modifying agents usually employed in the free radical polymerization ofunsaturated monomers containing an ethylenic double bond, such assulfur-containing agents represented by the alkyl mercaptans andxanthogen disulfides, are

preferably employed. Halogen-containing compounds such as carbontetrachloride may be utilized. These modifiers may be utilized tocontrol the molecular weight and molecular distribution of thecopolymers as well as the degree of branching and cross linking in thepolymer chains. The use of a modifying agent seems to be essential toobtain a soluble copolymer for cement applications. About 0.5 to 1.5parts of modifier are usually employed.

Good quality 1,1-difiuoro-2,2-dichloroethylene is preferred for use inpreparing these interpolymers. Inert impurities are not objectionablebut presence of hydrogen fluoride may interfere with the polymerizationreaction rate. The monomer should be protected from long and continuedexposure to moisture and air. Polymerization grade 1,3-butadiene andvinylidene chloride, 95 percent or better purity, are preferred butlower purity material may be used.

The interpolymers of this invention may be further modified if desired,by the addition of small amounts of organic plasticizers to the plastic,either in the latex stage or during later processing. Examples ofplasticizers useful for such a purpose are the organic esters such asdioctyl phthalate, dioctyl adipate, tricresyl phosphate and the like.

The unique class of plastic materials which are the products of thisinvention are adapted to a variety of uses. They may be used in moldingapplications as molded goods, as films, as adhesives, in coatingapplications and similar uses. They are especially useful inapplications where plasticized polymers are used under serviceconditions where the plasticizer would migrate into surrounding areas orwhere the plasticizer would be leached out, or other application where aflexible unplasticized polymer is desired.

Accordingly, this invention provides a new and useful class of plasticmaterials and methods for producing them. It is not intended thereforethat the invention be limited except by the spirit and scope of theappended claims.

We claim:

1. A plastic interpolymer prepared by polymerizing a monomeric mixturecomprising 25 to 45 mol percent of a 1,3-butadiene hydrocarbon, 35 to 55mol percent of a difiuorodichloroethylene and 10 to 35 mol percentvinylidene chloride.

2. The plastic interpolymer of claim 1 wherein the 1,3-butadienehydrocarbon is 1,3-butadiene.

3. The plastic interpolymer of claim 1 wherein thedifiuorodichloroethylene is 1,1-difiuoro- 2,2-dichloroethylene.

4. A plastic interpolymer prepared by polymerizing a monomeric mixturecomprising about mol percent 1,3-butadiene, to 50 mol percent1,1-difiuoro-2,2-dich1oroethylene and 20 to 35 mol percent vinylidenechloride.

5. A plastic interpolymer prepared by polymerizing a monomeric mixtureof 25 to mol percent of 1,3-butadiene, 35 to 55 mol percent of1,1-difiuoro-2,2-dichloroethylene and 10 to 35 mol percent of vinylidenechloride, said interpolymer comprising 20 to mol percent combined 1,1-difiuoro-2,2-dichloroethylene.

6. The method which comprises polymerizing a monomeric mixturecontaining 25 to 45 mol percent of a 1,3-butadiene hydrocarbon, 35 tomol percent of a difiuorodichloroethylene and 10 to 35 mol percent ofvinylidene chloride.

VERNON L. FOL'I. EARL J. CARLSON.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,584,126 Hanford Feb. 5, 1952 OTHER REFERENCES Lowry et al.,Ind. & Eng. Chem, vol. 41, No. 1, January 1949, pp. 146-155.

1. A PLASTIC INTERPOLYMER PREPARED BY POLYMERIZING A MONOMERIC MIXTURECOMPRISING 25 TO 45 MOL PERCENT OF A 1,3-BUTADIENE HYDROCARBON, 35 TO 55MOL PERCENT OF A DIFLUORODICHLOROETHYLENE AND 10 TO 35 MOL PERCENTVINYLIDENE CHLORIDE.